Search

Electrorheological fluids are new materials with good properties such as dielectric constant, dielectric loss or conductivity. These materials find practical applications in various industries. In this paper have been studied a ternary nanocomposite as rheological fluid based on Carboxymethyl starch and dimethylsulfoxide with feldspar particles. These nano composite was prepared by the two-step composite method. Firstly, the polar DMSO compound was directly intercalated into the interlayer of nano ferric oxide and then the intercalated complex was composite with CMS by the solution method. The composites, thus synthesized have been characterized by Fourier transfer infrared (FT-IR) spectrophotometer and X-ray diffraction. The morphology of these composites was studied by scanning electron microscopy.

The formation of hydrogen bonds and molecular dynamics of alkenylphenol derivatives has been investigated in solution using nuclear magnetic resonance. The results confirm formation of an N···H, O···H-type intramolecular hydrogen bond. The spin–lattice relaxation times (T 1) and activation energy of molecular dynamics have been investigated confirming the importance of relaxation times as a very sensitive tool for studying molecular mobility.

Two known iron(iii) complexes, [Fe(H2O)3(L1)]·xH2O (x = 4 (1), 5 (2)) and [Fe(H2O)3(L2)]·3H2O (3), bearing the basic forms of 5-chloro-3-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)-2-hydroxybenzenesulfonic acid (H3L1) and 3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxy-5-nitrobenzenesulfonic acid (H3L2), were prepared and used as homogeneous catalysts for cyanosilylation of a variety of aldehydes with trimethylsilyl cyanide leading to the corresponding cyanohydrin trimethylsilyl ethers. High yield (up to 98 %) was observed in the reaction catalyzed by 3 at room temperature in methanol.

Magnetic nanoparticles have been proposed for use as biomedical purposes to a large extent for several years. In this paper we discuss the preparation and characterization of superparamagnetic iron oxide (Fe3O4) nanoparticles (SPIONs) coated with acetyled – PAMAM dendrimers(Ac-PAMAM). Also, in the present study, the conjugate (Ac-PAMAM)/SPIO nanoparticles were exhaustivly studied as controlled-release systems for parenteral administration of a model drug 5-aminosalicyclic acid (mesalamine) and analyzed using various release kinetic studies. The nanoparticles thus synthesized have been characterized by a Fourier Transform Infrared (FTIR) spectrophotometer and with X-ray diffraction. The morphology of these nanoparticles was studied by scanning electron microscopy (SEM).

Maleic anhydride–allyl propionate–styrenе terpolymer has been modified with tri-ethanolamine in order to prepare a new cross-linked functional polymer sorbent. The sorption behaviors of UO 2 2+ ions on the optimum sorption conditions were determined. The synthesized cross-linked polymer has a network structure that contains carboxylic acid, carbonyl, hydroxyl, amine and ester groups; all of which are capable of interacting with metal ions. The maximum capacity of the sorbent for uranyl ions has been measured as 2.5 mmol g − 1 (675 mg UO 2 2+ g − 1 ). Langmuir and Freundlich isotherm constants and correlation coefficients for the present system have been compared and the Langmuir model provides the best fit. Uranyl ions are desorbed from the sorbent by treatment with 10% HCl, HNO 3 or H 2 SO 4 .

Magnetic nanoparticles have been proposed for use as biomedical purposes to a large extent for several years. The development of techniques that could selectively deliver drug molecules to the diseased site, without a concurrent increase in its level in healthy tissues, is currently one of the most active areas of cancer research. The conjugate carboxymethyl starch (CMS)/SPIO nanoparticles were prepared by chemical reaction. Several parameters including the drug/polymer ratios in range of 1:14 were examined to optimize formulation. The size distribution and morphology of nanoparticles and in vitro release profile in phosphate buffer medium (pH 7.4) during 12 h were then investigated. The magnetic NPs prepared in this study were spherical with a relatively mono-dispersed size distribution. The conjugate carboxymethyl starch (CMS)/SPIO nanoparticles were exhaustively studied as controlled-release systems for parenteral administration of a model drug 5-aminosalicyclic acid (mesalamine) and analyzed using various release kinetic studies.

The copper(II) complex with 3-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)pentane-2,4-dione (H3L) is studied, and its crystal structure is studied by X-ray diffraction analysis. The crystals of [Cu(H2O)2]2(μ-L)2[Cu(H2O)4] (I) are triclinic (space group P\( \bar 1 \)) at 100 K, a = 7.085(3), b = 10.373(5), c = 12.265(6) A, α = 0.842(5)°, β = 104.996(6)°, γ = 99.156(6)°, Z = 1). The C=O and NH groups of hydrazone and the OH and SO3H groups from the aromatic moiety of the molecule are involved in coordination with the copper(II) atom. In the centrosymmetric trinuclear molecule the central Cu(2) atom has the coordination number six, and the terminal Cu(1) atoms have the coordination number five. The thermal properties of complex I are studied. The complex formation of copper(II) with the H3L ligand in an aqueous solution at temperatures 298 ± 0.5, 308 ± 0.5, and 318 ± 0.5 K is studied by potentiometric titration. The standard thermodynamic functions of the complex formation are determined.

In this paper, preparation and characterization of superparamagnetic nanoparticles and their polymer composites prepared by varing doping level of conducting polymer and their microwave absorption studies at radar system in 8–12 GHz frequency range have been discussed. These composites are conducting polymers have been widely used because of their lower density as well their good environmental stability as in the case of polyaniline (PAN). In the present work, in situ polymerization of aniline was carried out in the presence of 30 mole% Fe3O4 nanoparticles to synthesize polyaniline/Fe3O4(PAN/Fe3O4) composites in epoxy resin matrix. The composites, thus synthesized have been characterized by infrared (IR) spectroscopy and X-ray diffraction. The morphology of these composites was studied by scanning electron microscopy. The measurement of % absorption was carried out in X and K band microwave region.

The synthesis and anion binding properties of a neutral macrocyclic receptor bearing H-bond donor coordination sites are described. The anion binding studies by use of UV-vis and 99Tc NMR methods revealed that the receptor can coordinate perrhenate and pertechnetate in dimethylsulfoxide and chloroform solutions with the relatively high binding constants, viz. log Ka > 4. The coordination mode of the perrhenate to the receptor was determined by a single-crystal X-ray diffraction analysis.

Natural polymers are considered high value polymeric materials because of their potential as biocompatible materials with medical applications. The chemical modification of natural polymers by grafting has received considerable attention in recent years because of the wide variety of monomers available. As the first part of a continued research on conversion of carboxymethyl starch (CMS) to useful biopolymer-based materials, large numbers of carboxylic functional groups were introduced onto CMS by grafting with polymethacrylic acid (PMAA). Free radical graft copolymerization was carried out at 70 °C, bis-acrylamide as a crosslinking agent and persulfate as an initiator. Equilibrium swelling studies were carried out in enzyme-free simulated gastric and intestinal fluids (SGF and SIF, respectively). Also, the sodium dicofenac as a model drug was entrapped in these nano-gels and the in vitro release profiles were established separately in both enzyme-free SGF and SIF. The drug release was found to be faster in SIF. The drug-release profiles indicate that amount drug release depends on their degree of swelling, and crosslinking. This hydrogel converted to nano by freeze-drying method and characterized by scanning electron microscopy, differential scanning calorimetry and FT-IR spectrometry.

The interaction between 1-furyl-1,2,3,4-tetrahydroisoquinolines and unsaturated acids derivatives (acryloyl, methacryloyl, and crotonoyl chloride, maleic and citraconic anhydride) was studied. It was shown that the reaction proceeds via amide formation and subsequent intramolecular Diels–Alder reaction of the furan (IMDAF). The [4þ2] cycloaddition proceeded under mild reaction conditions

The alkylation of some representatives of β-dicarbonyl compounds by 1,4-dibromo-2-butene and ethyl 2,3-dibromopropionate was investigated.

In spite of its impressive record in medicinal chemistry, the role of barbituric acid H 3 BA (pyrimidine-2,4,6(1 H ,3 H ,5 H )-trione) in coordination, organometallic and supramolecular chemistries has not yet been analyzed and reviewed. However, H 3 BA can be readily functionalized and provides rich opportunities to create coordination bonds and non-covalent interactions. Thus, derivatives of H 3 BA (barbituric acids, BAs) are widely used for the preparation of a wide range of complexes with various metals of almost all groups of the periodic table. The review systematizes information on the synthesis, tautomerism, acid–base properties of BAs and their use for the construction of organometallic and coordination compounds, as well as coordination polymers and supramolecular assemblies. The role of different metal ions and the structure of BAs in directing the preparative pathways and tuning particular structural properties of the resulting compounds are discussed. Some valuable applications of BAs, in particular in the construction of molecular receptors, magnetic and nonlinear optic materials, bioactive compounds, drug cocrystal design, catalysis and photochemistry are also envisaged.

Have been studied the electrical properties of Nano-Si/U3O8 composites. Was found the change of electrical conductivity of Nano-Si/U3O8 composite properties mostly occurs via mechanism of spasmodic conductivity. The analysis of experiment results of dependency of electro physical properties of Nano-Si/U3O8 composite from frequency shows that the changes occur due to polarization of components on interphase border. In such kind materials the dielectric relaxation can be determined by exact impedance of ratio of real and imaginary content.

Reaction of uranyl nitrate hexahydrate with 3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxybenzenesulfonic acid (H3L) and bis((E)-phenyldiazenyl)methanone (bpm) yields mononuclear zwitterionic uranyl complex, [UO2(HL)(bpm)(H2O)2]∙3H2O (1), which was characterized by IR, ESI-MS spectroscopies, and elemental and X-ray single-crystal analyses. In 1, the uranium center is in distorted pentagonal bipyramidal geometry with HL2 − and bpm ligands coordinated in equatorial plane. The coordination to uranyl and intramolecular hydrogen bonding assist the tautomerization of bpm and formation of zwitterion.

A [12]metallacrown-6 palladium cluster, [Pd6(μ2-SCH2CH2OH)12] (1), was obtained upon reaction of Pd[(NH3)4]Cl2 with 2-mercaptoethanol in water solution. 1 was characterized by IR spectroscopy, elemental and single crystal X-ray diffraction analyses. Within the molecule, the six palladium atoms are united by disulfobridges (from twelve thiolate anions), forming almost ideal plane hexagon. Each palladium is surrounded by four sulphur atoms in an approximately square planar fashion, with Pd–S distances of 2.3094(5)–2.3378(5) A, while the shortest Pd–Pd distance is 3.0931(2)–3.1098(2) A. The clusters are interconnected by hydrogen bonds through hydroxy-groups of thiolate ligands forming a supramolecular infinite 3D structure.

One-pot template condensation of CCl3CN with ammonia on a metal source [MnCl2·4H2O, FeCl3·6H2O or Co(CH3COO)2·4H2O] in DMSO led to the formation of tris{2,4-bis(trichloromethyl)-1,3,5-triazapentadienato}-M(III) complexes, [M{NHC(CCl3)NC(CCl3)NH}3]·n(CH3)2SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)], which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1–3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) 3.155 (2) > 3.133 (1) A]. Compounds 1–3 and the related di(triazapentadienato)-Cu(II) complex [Cu{NHC(CCl3)NC(CCl3)NH}2]·2(CH3)2SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 × 103 after 1 h of low power (10 W) MW irradiation.

Reaction of binucleophiles with 1,4- and 1,3-bis(2-chloro-2-cyanovinyl)benzenes, synthesized using a catalytic olefination of terephthalic and isophthalic aldehydes, gave high yields of aminopyrazoles, 3-amino-5-arylthiophene-2-carboxylic acid esters, and 2,4-diamino-6-arylpyrimidines.

Template condensation of CCl 3 CN and ammonia on zinc(II) (used as acetate) afforded, in one step, bis(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-zinc(II) 1 , which was characterized by elemental analysis, ESI-MS, IR and X-ray single-crystal analysis. The complex 1 was shown to be an effective catalyst in the nitroaldol (Henry) reaction, providing high yields (up to 99%) and good diastereoselectivities ( threo/erythro up to 3:1) at ambient conditions.

The main objective of this study is development of chitosan supramolecular gels to utilize for oral delivery of insulin. Chitosan (CS) blended dextran sulfate (DS) matrix as nanogels were characterized by scanning electron microscopy and FT-IR. Equilibrium swelling studies were carried out in enzyme-free simulated gastric and intestinal fluids (SGF and SIF, respectively). Insulin entrapped in these gels and in vitro release profiles were established. In vitro release of insulin was also evaluated. The CS-DS gels have been developed based on the modulation of ratio show promise as a system for controlled delivery of the insulin to the stomach.

Molecular dynamics of cyclohexenone derivatives of (2E,4E)-1-(2-hydroxy-5-methylphenyl)-5-phenyl-2,4-pentadiene-1-one (chalcone) has been investigated in solutions using NMR. The results confirm the formation of O-H⋯O intramolecular hydrogen bond and the presence of keto–enol tautomeric transitions in the (E)-6-acetyl-3-(2-hydroxy-5-methylphenyl)-5-styryl cyclohex-2-en-1-one. The free energy of activation for the keto–enol tautomeric transitions has been calculated. The keto–enol tautomerism in the investigated compound has been also confirmed by chemical method. Copyright © 2013 John Wiley & Sons, Ltd.

Cycloalkenes react with di(2-pyridyl) diselenide in the presence of antimony pentachloride with the formation of products of the selenenylating electrophile cycloaddition at the multiple bond. The final products of heterocyclization, chloroantimonates(III) of 2,3-dihydro[1,3]selenazolo[3,2-a]pyridinium derivatives were isolated.

A reaction of styrene with the di(2-pyridyl) diselenide—antimony pentachloride system furnishes 2,3-dihydro[1,3]selenazolo[3,2-a]pyridinium chloroantimonates(III) and (V), the products of cycloaddition of the selenylating agent at the multiple bond.

The title compound, [Cu(C4H2Cl6N3)2], was obtained by the reaction of CCl3CN with ammonia in presence of CuCl. The CuII atom is located about an inversion centre. The molecule consists of three planar units (one central square CuN4 and two C2N3 fragments), adopting a staircase-like structure. The six-membered metallocycles have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triazapentadienyl ligands by 0.246 (5) Å. The ipso-C atoms of the CCl3 substituents are slightly out of the 1,3,5-triazapentadienyl planes by 0.149 (6) and −0.106 (6) Å. The CCl3 groups of each 1,3,5-triazapentadienyl ligand are practically in the energetically favourable mutually eclipsed conformation. In the crystal, the molecules are packed in stacks along the a axis. The molecules in the stacks are held together by two additional axial Cu...Cl interactions of 3.354 (2) Å. Taking the axial Cu...Cl interactions into account, the CuII atom exhibits a distorted [4 + 2]-octahedral coordination environment. The stacks are bound to each other by weak intermolecular attractive Cl...Cl [3.505 (2)–3.592 (3) Å] interactions.

The present work is devoted to preparation of track membranes by irradiation of polymeric film of isotactic Polypropylene (PP) with accelerated heavy ions of xenon (energy 1.3 MeV/nucl, flow density 10 8 up to 10 10 ion/sm 2 ). The further chemical treatment of irradiated film with KOH (Potassium Hydroxide) solution leads to formation of pores in the polymeric film. It was found that the optimal conditions of track etching of heavy ions in polymer have been studied by the process of pores etching in polymeric film by Atomic Force Microscopy (AFM) method. It has been found out by AFM method, that increase of Xe ions beam density from 10 8 up to 10 10 ion/sm 2 leads to increasing of number, diameter and depth of pores on the surface and from within of polypropylene film. The influence of alkali concentration and temperature on size and depth of pores in the polymeric film has been detected. It has been shown that increasing of concentration of alkali 0.25 M up to 1.5 M and temperature up to 80 ° С lead to decreasing of diameter and depth of pores in polypropylene matrix.

The main aim of this research is to study the in vitro photocytotoxicity and cellular uptake of biodegradable polymeric nanoparticles loaded with photosensitizer mTHPP. As the first part of a continued research on conversion of N-sulfonato-N,O-carboxymethylchitosan (NOCCS) to useful biopolymer-based materials, large numbers of carboxylic functional groups were introduced onto NOCCS by grafting with polymethacrylic acid (PMAA). The free radical graft copolymerization was carried out at 70°C, bis-acrylamide as a cross-linking agent and persulfate as an initiator. These results show that the nanoparticles have high loading capacity and stability. These nanoparticles are suitable as carriers for photodynamic therapy in vivo.

Hybrid materials, which consist of organic-inorganic materials, are of profound interest owing to their unexpected synergistically derived properties. Aluminum oxide (Al2O3) nanoparticles/polymer composites have been produced using a one-system polymer synthesis. The linear polymer, poly(methyl methacrylate) (PMMA,MW=15,000 g/mol) is applied for the stabilization of Al2O3nanoparticles. Fourier transfer infrared analysis data and scanning electron microscopy image reveal that the core shell structure of the Al2O3/PMMA nanocomposite has been synthesized. The ratio of concentration of the capping polymer material to the concentration of the Al2O3precursor could control the size of Al2O3nanoparticles. With specific concentration of the reductant, the core-shell nanostructure could be fluctuated in order.

The molecule of the title compound, C22H26O2, exhibits Ci molecular symmetry with a crystallographic inversion centre at the mid-point of the central C—C bond. A kink in the molecule is defined by the torsion angle of 66.7 (2)° about this central bond of the alkyl bridge.

In the title compound, C20H26N2OS, four non-H atoms of the thiourea unit are approximately planar (r.m.s. deviation = 0.005 Å); the phenyl and benzene rings are twisted out of this plane by 28.55 (7) and 60.00 (7)°, respectively. An intramolecular N—H...O hydrogen bond occurs. The hydroxy group is hydrogen bonded to the double-bond S atom of an inversion-related molecule, generating a hydrogen-bonded dimer in the crystal structure.

In the title compound, [Cu(C(8)H(4)F(3)O(2)S)(2)(C(10)H(14)N(2)O)], the Cu(II) atom exists in a distorted CuNO(4) square-pyramidal geometry; the metal atom lies above a square plane defined by four O atoms of the two chelating anionic ligands, displaced in the direction of the axial occupant, the pyridine N atom, by 0.179 (1) Å. Weak inter-molecular C-H⋯O and C-H⋯F hydrogen bonding is present in the crystal structure. One thienyl ring is disordered over two orientations in an occupancy ratio of 0.69 (1):0.31.

The six-membered oxacyclo-hexene ring of the title compound, C(13)H(14)N(2)O(2)S, is fused with the benzene ring and the quarternary C atom lies above the plane of the benzene ring by 0.229 (8) Å, whereas the methine C atom (which bears the acetyl substituent) lies below this plane by 0.595 (8) Å. The oxacyclo-hexene ring is also fused with the sofa-shaped 2,6-diaza-cyclo-hexa-none ring. The methine C atom that belongs to both six-membered rings lies above the mean plane of the other five atoms (r.m.s. deviation = 0.077 Å) by 0.759 (5) Å. In the crystal, N-H⋯S hydrogen bonds link adjacent mol-ecules into a linear chain.

In the title 2-propanol derivative, C17H27ClO2, the two tert-butyl groups both have one methyl C atom lying in the plane of the aromatic ring. In the crystal, the phenol group forms a hydrogen bond to the hydroxy O atom belonging to the alkyl substituent of an adjacent molecule, forming a chain along the ac diagonal. The Cl atom is disordered over two positions in a 0.73 (4):0.27 (4) ratio.

The title compound, C(17)H(27)NO, features a bufferfly-shaped substituted 2-propanol having an aromatic ring on the 1-carbon and a piperidine ring on the 3-carbon. The piperidine ring adopts a chair conformation and its N atom shows a trigonal coordination. In the crystal, the hy-droxy group inter-acts with the N atom of an inversion-related mol-ecule, generating an O-H⋯N hydrogen-bonded dimer.

The title compound, C(10)H(11)Cl(5)O, is a chiral mol-ecule with two stereogenic centres. However, it crystallizes as a racemate. One of enanti-omers reveals the relative configuration (2S*,5R*). The cyclo-hexene ring adopts a half-chair conformation.

Local drug delivery strategies have gained momentum recently as a promising modality in cancer therapy. In order to deliver Letrozole (LTZ) at the tumor site in therapeutically relevant concentrations, acetyl-polyamidoamine (Ac-PAMAM)–thiolated chitosan (TCS) films were fabricated. LTZ could be loaded at 31% wt/wt in films, which were translucent and flexible. Physicochemical characterization of LTZ via thermal technique revealed information on solid-state properties of LTZ as well as thiolated chitosan in films. While thiolated chitosan was in amorphous form, LTZ seemed to be present in both amorphous and crystalline forms in film. The lack of formulation-induced local inflammatory responses of LTZ-acetyl-polyamidoamine (Ac-PAMAM)–thiolated chitosan (TCS) films a new paradigm for localized chemotherapy based on breast delivery systems.

In the title compound, C25H28N2O4, the cyclohexene ring adopts a half-chair conformation and the dihedral angle between the aromatic rings is 59.44 (11)°. In the crystal, a weak intermolecular N—H...O hydrogen bond occurs.

The title molecule, C21H30N2O5, is chiral with four stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the relative configuration rac-(6S*,7R*,8R*,9S*). The ethyl fragment of the ethoxycarbonyl group at position 6 is disordered in a 0.46 (3):0.54 (3) ratio. The crystal structure features intermolecular N—H...O. Intramolecular O—H...N and N—H...O hydrogen bonds also occur.

The main objective of this study was to develop a local, oral mucoadhesive metronidazole benzoate (MET) delivery system that can be applied and removed by the patient for the treatment of periodontal diseases. The results of present study revealed that the retention time of MET at its absorption site could be increased by formulating it into nanoparticles using thiolated chitosan (TCS)–poly(methacrylic acid) (PMAA). The nanoparticles of MET prepared from TCS–PMAA may represent a useful approach for targeting its release at its site of absorption, sustaining its release and improving its oral availability.

The structure of the title compound, C17H19NO3, is of interest with respect to antibacterial properties, antibiotic properties and biological activity. The structure displays intermolecular O—H...N hydrogen bonding.

The organic molecule in the title hydrate, C9H9N3O3·H2O, was obtained by the condenstation of salicylic aldehyde with urea in acetonitrile. The oxazine ring adopts a slightly distorted sofa conformation, with the N atom deviating from the plane passing through the other atoms of the ring by 0.267 (2) Å. The crystal structure displays intermolecular N—H...O and O—H...O hydrogen bonding.

The structure of the title compound, C17H21N2O2+·Cl−, is of interest with respect to its biological activity. The title compound comprises an organic cation and a chloride anion in the asymmetric unit. The positive charge is localized in a pyrazole moiety forming a pyrazolium cation. The structure displays intermolecular O—H...Cl and N—H...Cl hydrogen bonding.

A new straightforward synthesis of 8,10a-epoxypyrido[2,1-a]isoindoles and their 7-carboxylic acids from 2,6-difuryl-substituted piperidin-4-ones and maleic anhydride or acryloyl chloride via the intramolecular Diels-Alder reaction has been demonstrated. It has been shown that a one-stage synthesis of the title compounds can be performed under mild conditions and with high levels of regio- and stereoselectivity from easily accessible 2-furylpiperidines.

The alkylation of some representatives of β-dicarbonyl compounds by 1,4-dibromo-2-butene and ethyl 2,3-dibromopropionate was investigated.

A new straightforward synthesis of 8,10a-epoxypyrido[2,1-a]isoindoles and their 7-carboxylic acids from 2,6-difuryl-substituted piperidin-4-ones and maleic anhydride or acryloyl chloride via the intramolecular Diels-Alder reaction has been demonstrated. It has been shown that a one-stage synthesis of the title compounds can be performed under mild conditions and with high levels of regio- and stereoselectivity from easily accessible 2-furylpiperidines.

In the title compound, [Cu(C8H4F3O2S)2(C10H14N2O)], the CuII atom exists in a distorted CuNO4 square-pyramidal geometry; the metal atom lies above a square plane defined by four O atoms of the two chelating anionic ligands, displaced in the direction of the axial occupant, the pyridine N atom, by 0.179 (1) A. Weak inter­molecular C—H⋯O and C—H⋯F hydrogen bonding is present in the crystal structure. One thienyl ring is disordered over two orientations in an occupancy ratio of 0.69 (1):0.31.

The macrocycle of the title compound, C36H24N4O3S·2CHCl3, contains a rigid framework with the nitrogen and oxygen heteroatoms pointing in towards the center of the macrocyclic cavity. The macrocycle is essentially planar (r.m.s. deviation = 0.027 Å) except for the thiophene ring. The dihedral angle between the thiophene ring plane and the mean plane of the central macrocyclic core including all atoms except sulfur is 21.6 (1)°. Four intramolecular hydrogen bonds occur: two are between the amide hydrogen atoms and the Schiff base nitrogen atoms, while the others are between the amide hydrogen atoms and the sulfur atom of the thiophene. The two solvate chloroform molecules are bound to the carbonyl oxygen atoms of the ligand by weak C—H...O hydrogen bonding. In addition, the structure reveals intermolecular Cl...Cl close contacts [3.308 (2), 3.404 (2) and 3.280 (2) Å] between the chloroform solvate molecules. In the crystal, the macrocycles form layers parallel to (101), with an interlayer distance of 3.362 (3) Å. This short distance is determined by the stacking interactions between the amide carbonyl and imine fragments of neighboring ligands.

The title molecule, C21H25NO7, has four stereogenic centres and crystallized as a racemate. It consists of enantiomeric pairs with the relative configuration rac-(1R*,2S*,3R*). The cyclohexenone ring adopts an envelope conformation; the dimethyl-substituted C atom lies 0.640 (1) Å out of the mean plane formed by the rest of the ring atoms (r.m.s. deviation = 0.016 Å). The oxacyclohexene ring adopts a half-chair conformation, the hydroxy- and carboxyl-substituted C atoms lying −0.336 (1) and 0.419 (1) Å, respectively, out of the mean plane formed by the rest of the ring atoms (r.m.s. deviation = 0.002 Å). In the crystal, O—H...O hydrogen bonds link the molecules into a chain along the c-axis direction.

The title compound, C14H13NO2, adopts the enol–imine tautomeric form, with an intramolecular O—H...N hydrogen bond which generates an S(6) ring motif. The dihedral angle between the aromatic rings is 7.85 (7)°. The crystal structure is stabilized by O—H...O, O—H...N and C—H...O hydrogen bonds, forming a two-dimensional array that stacks along the a axis. In addition, a C—H...π interaction contributes to the stabilization of the crystal packing.